EP1423195A1 - Catalyseurs de metathese de carbene metallique de ruthenium ou d'osmium hexacoordonnes - Google Patents

Catalyseurs de metathese de carbene metallique de ruthenium ou d'osmium hexacoordonnes

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Publication number
EP1423195A1
EP1423195A1 EP02791535A EP02791535A EP1423195A1 EP 1423195 A1 EP1423195 A1 EP 1423195A1 EP 02791535 A EP02791535 A EP 02791535A EP 02791535 A EP02791535 A EP 02791535A EP 1423195 A1 EP1423195 A1 EP 1423195A1
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Prior art keywords
group
substituted
alkyl
unsubstituted
compound
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EP02791535A
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German (de)
English (en)
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EP1423195A4 (fr
EP1423195B1 (fr
Inventor
Robert H. Grubbs
Melanie S. Sanford
Jason L. Moore
Jennifer A. Love
Tina M. Trnka
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California Institute of Technology CalTech
Materia Inc
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California Institute of Technology CalTech
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Priority claimed from US09/948,115 external-priority patent/US6610626B2/en
Priority claimed from US10/017,489 external-priority patent/US6759537B2/en
Priority claimed from US10/107,531 external-priority patent/US6838489B2/en
Priority claimed from US10/138,188 external-priority patent/US20030083445A1/en
Application filed by California Institute of Technology CalTech filed Critical California Institute of Technology CalTech
Publication of EP1423195A1 publication Critical patent/EP1423195A1/fr
Publication of EP1423195A4 publication Critical patent/EP1423195A4/fr
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    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
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    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
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    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/825—Osmium
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same.
  • the inventive catalysts are of the formula
  • M is ruthenium or osmium
  • X and X 1 are the same or different and are each independently an anionic ligand
  • L, L 1' and L 2 are the same or different and are each independently a neutral electron donor ligand; and, R and R 1 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, Ci-C 2 o carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C ! -C 2 o alkylthio, Ci-C 2 o alkylsulfonyl, C ! -C 2 o alkylsulfinyl, and silyl.
  • each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci-Cio alkyl, C ⁇ -C 10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -C 5 alkyl, -Cs alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate. halogen, alcohol, sulfonic acid, phospbine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
  • L and L are pyridine and L is a phosphine or an N- heterocyclic carbene ligand.
  • N-heterocyclic carbene ligands include:
  • R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C -C 20 alkynyloxy, aryloxy, C -C 20 alkoxycarbonyl, C 1 -C 0 alkylthio, C 1 -C 20 alkylsulfonyl. C 1 -C 20 alkylsulfmyl and silyl.
  • each of the R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 and R 1 substituent group may be substituted with one or more moieties selected from the group consisting of -Cio alkyl, C 1 - 0 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -Cs alkyl, CrC 5 alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide. acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
  • NHC ligand to the hexacoordinated ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. Because the NHC-based hexacoordinated complexes are extremely active, the amount of catalysts that is required is significantly reduced.
  • the present invention generally relates to ruthenium and osmium carbene catalysts for use in olefin metathesis reactions. More particularly, the present invention relates to hexacoordinated ruthenium and osmium carbene catalysts and to methods for making and using the same.
  • the terms "catalyst” and “complex” herein are used interchangeably.
  • M is ruthemum or osmium
  • X and X 1 are each independently any anionic ligand
  • L and L 1 are each independently any neutral electron donor ligand; R and R 1 are the same or different and are each independently hydrogen or a substituent selected from the group consisting of -C 2 o alkyl, C 2 -C 20 alkenyl, C 2 -C 0 alkynyl, aryl, -C2 0 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 0 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 0 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, and silyl.
  • each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci- o alkyl, Ci-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a Ci-C 5 alkyl, -C 5 alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulf nic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
  • the catalysts of the present invention are similar in that they are Ru or Os complexes; however, in these complexes, the metal is formally in the +2 oxidation state, and has an electron count of 18 and are hexacoordinated.
  • These catalysts are of the general formula:
  • M is ruthenium or osmium
  • X and X 1 are the same or different and are each independently any anionic ligand
  • L. L 1' , and L 2 are the same or different and are each independently any neutral electron donor ligand;
  • R and R 1 are the same or different and are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 0 alkyl, C 2 -C 20 alkenyl, C 2 -C 0 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 0 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, -C20 alkylsulfinyl, and silyl.
  • each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci-Cio alkyl, Ci-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -C 5 alkyl, -Cs alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
  • the hexacoordinated complex provides several advantages over the well-known pentacoordinated complexes.
  • the hexacoordinated complexes have greater air stability in the solid state because they are coordinatively saturated. Due to the lability of the additional ligand, e.g. pyridines, the complexes initiate faster than the phosphine based pentacoordinated species. Slow initiation means that only a small amount of complex is actually catalystically active thereby wasting much of the added complex. With faster initiators, catalyst loading is lowered.
  • the pentacoordinated benzylidene with triphenylphosphme as its phosphine ligand can be prepared in higher yield and with greater purity using the hexacoordinated complex.
  • the pentacoordinated benzylidene with P(/?-CF 3 C 6 H 4 ) 3 as its phosphine ligand is inaccessible through existing routes. Without being bound by theory, it is believe that this is because it would require the substitution of a stronger donor ligand with a weaker donor ligand. Substitution of the anionic ligands of the hexacoordinated complexes is much more rapid than with the corresponding pentacoordinated species (e.g. phosphine bound). Without being bound by theory, it is believed that this results from the requirement of ligand dissociation before anionic ligand substitution. Thus complexes with fast dissociation of their neutral electron donor ligands will undergo faster substitution.
  • the catalysts of the invention are also useful for ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), ADMET. and cross- metathesis.
  • ROMP ring-opening metathesis polymerization
  • RCM ring-closing metathesis
  • ADMET ADMET.
  • cross- metathesis The synthesis and polymerization of olefins via these metathesis reactions can be found in, for example, U.S. Application Nos. 09/891,144 entitled: "Synthesis of Functionalized and Unfunctionalized Olefins, filed June 25, 2001, and U.S. Application No. 09/491,800, the contents of each of which are incorporated herein by reference.
  • Preferred embodiments of the catalysts of the invention possess at least one NHC ligand attached to the metal center, as illustrated by the following general formula:
  • the R substituent is hydrogen and the R 1 substituent is selected from the group consisting of -C 20 alkyl, C 2 -C 20 alkenyl, and aryl.
  • the R 1 substituent is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of -C 5 alkyl, -C 5 alkoxy, phenyl, and a functional group.
  • R 1 is phenyl or vinyl substituted with one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, -NO 2 , - NMe 2 , methyl, methoxy and phenyl.
  • the catalyst is of the general formula:
  • R' and R" are preferably independently hydrogen or phenyl but can be selected from any of the groups listed for R or R 1 .
  • X and X 1 are each independently hydrogen, halide, or one of the following groups: C ⁇ -C 2 o alkyl, aryl, C1-C2 0 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C o alkylsulfonate, -C2 0 alkylthio, C C 2 o alkylsulfonyl, or C C 2 o alkylsulfinyl.
  • X and X 1 may be substituted with one or more moieties selected from the group consisting of -Cio alkyl, d-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from halogen, C C 5 alkyl, Ci-C 5 alkoxy, and phenyl.
  • X and X 1 are halide, benzoate, Q-Cs carboxylate, -C 5 alkyl, phenoxy, -C 5 alkoxy, -Cs alkylthio, aryl, and C ⁇ - C 5 alkyl sulfonate.
  • X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 . CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
  • X and X 1 are each chloride.
  • L, L , L and L may be any appropriate monodentate or multidentate neutral electron donor ligands.
  • Multidentate neutral electron donor ligands include bidentate, tridentate, or tetradentate neutral electron donor ligands, for example.
  • L, L 1 , L 1' and L 2 are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphorate, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether, or any derivatives therefrom. At least one
  • L, L , L and L may also be an N-heterocyclic carbene ligand.
  • Preferred embodiments include complexes where both L and L are either the same or different NHC ligands.
  • At least one of L, L 1 , L 1' and L 2 is a phosphine of the formula PR 3 R 4 R 5 , where R 3 , R 4 , and R 5 are each independently aryl or Ci-do alkyl, particularly primary alkyl, secondary alkyl or cycloalkyl.
  • at least one of L, L 1 , L 1 ' and L 2 is each selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3 , and -P(phenyl) 3 .
  • L, L 1 , L 1 and L 2 are each NHC ligand.
  • L is an NHC
  • L 1 is P(cyclohexyl) 3 or -P(cyclopentyl) 3
  • L 1 and L 2 are each heterocyclic ligands, optionally aromatic, or together form a bidenatate ligand.
  • L 1 and L 2 are each independently pyridine or a pyridine derivative.
  • NHC ligands examples include ligands of the general formulas:
  • R, R 1 , R', R", R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently hydrogen or a substituent selected from the group consisting of d-C 20 alkyl, C 2 -C 2 o alkenyl, C 2 - C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 2 o alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 2 o alkynyloxy, aryloxy, C 2 -C 0 alkoxycarbonyl, C ⁇ -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfmyl, and silyl.
  • each of the R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 , and R 1 substituent group may be substituted with one or more moieties selected from the group consisting of d-do alkyl, Ci-do alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a Ci-Cs alkyl, C1-C 5 alkoxy, and phenyl.
  • any of the catalyst ligands may further include one or more functional groups.
  • Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide. acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
  • R 6 , R 7 , R 8 and R 9 are independently selected from the group consisting of hydrogen, phenyl, or together form a cycloalkyl or an aryl optionally substituted with one or more moieties selected from the group consisting of Ci-do alkyl, d-do alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen; and R 10 and R 11 are each is independently d- do alkyl or aryl optionally substituted with d-C 5 alkyl, d-C 5 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether
  • R and R are both hydrogen or phenyl, or R and R together form a cycloalkyl group;
  • R 8 and R 9 are hydrogen and R 10 and R 11 are each either substituted or unsubstituted aryl.
  • R 10 and R 11 are the same and each is independently of the formula:
  • R 12 , R 13 , and R 14 are each independently hydrogen, d-do alkyl, d-do alkoxy, aryl, or a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen, hi especially preferred embodiments, R 12 , R 13 , and R 1 are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen. In the most preferred embodiments, R 12 , R 13 , and R 14 are the same and are each methyl.
  • R , R , R , and R are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 0 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C ⁇ -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, d-C 2 o alkylthio, d-C 20 alkylsulfonyl and d-C 2 o alkylsulfinyl.
  • Lnidazolidine ligands are also referred to as imidizol-2-ylidene ligands.
  • neutral electron donor ligands include ligands which are derived, for example, from unsubstituted or substituted heteroarenes such as furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine, gamma-pyran, gamma-thiopyran, phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bis, bis
  • heteroaralkyl, aralkenyl and heteroaralkenyl in turn are unsubstituted or substituted by one of the above-mentioned substituents; and y is 1 and M is a monovalent metal or y is 1/2 and M is a divalent metal.
  • metal and corresponding cations refer to an alkali metal, for example Li, Na or K, an alkaline earth metal, for example Mg, Ca or Sr, or Mn, Fe, Zn or Ag, and corresponding cations.
  • Lithium, sodium and potassium ions, with their salts, are preferred.
  • NH 2 monoamino, diamino, carbamide, carbamate, carbohydrazide, sulfonamide, sulfohydrazide and aminocarbonylamide correspond preferably to a group R 8 C(O)(NH) p N(R 9 )--, -C(O)(NH) p NR 8 R 9 , R 8 OC(O)(NH) p N(R 9 ) ⁇ , R 8 R 40 NC(O)(NH)p N(R 9 ) ⁇ , -OC(O)(NH) p R 8 R 9 , --NO C O) ⁇ H) P NR 8 R 9 , R 8 S(O) 2 (NH) P N(R 9 )-; - S(O) 2 (NH) p NR 8 R 9 ; R 8 R 40 NS(O) 2 N(R 9 ) ⁇ or --NR ⁇ O) 2 NR 8 R 9 , in which R 8 , R 9 and io independently of one another are
  • the sulfonyl substituent is, for example, of the formula R 10 --SO 2 -- in which R 10 is d- C t2 alkyl, C -Ci 2 cycloalkyl, d-C ⁇ heterocycloalkyl, C 6 -do aryl, C 5 -C 9 heteroaryl, C 7 -C ⁇ aralkyl or C 6 -C 10 heteroaralkyl which are unsubstituted or substituted by one or more substituents selected from the group consisting of OH, halogen, C(O)OR sl , OC(O)R s4 , C(O)R S2 , nitro, NH 2 , cyano, SO 3 Z y , OSO 3 Z y , NR 20 SO 3 Z y , C C 12 alkyl, C 2 -C 12 alkenyl, d-C 1 alkoxy, C 3 -C 12 cycloalkyl, C 3 -C 12
  • a more preferred group of compounds is formed when L and L independently of one another are pyridyl which is unsubstituted or substituted by one or more substituents from the group consisting of d-C 12 alkyl, C 2 -C ⁇ heterocycloalkyl, C 5 -C heteroaryl, halogen, monoamino, diamino and -C(O)H. Examples are
  • Examples are:
  • L 2 and L 1 are each independently selected from the group consisting of:
  • R is selected from the group consisting of hydrogen or a substituent selected from the group consisting of d-C 2 o alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, d-C 20 carboxylate, Ci-C 20 alkoxy, C 2 -C 20 alkenyloxy, d-do alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, d-C 2 o alkylthio, Ci-C 20 alkylsulfonyl, d-C 2 o alkylsulfinyl, and silyl.
  • the R group may be substituted with one or more moieties selected from the group consisting of d-C 10 alkyl, d-do alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a d-C 5 alkyl, d-C 5 alkoxy, and phenyl.
  • any of the heterocycles may further include one or more functional groups.
  • R is selected from the group consisting of d-C 2 o alkyl, aryl, ether, amine, halide, nitro, ester and pyridyl.
  • complexes 1-4 and 44-48 are used to make the preferred embodiments 5- 29 and 49-83 of the inventive complex:
  • L is an NHC, preferably an imidazolidine ligand, and L and L ' are pyridines.
  • the complexes can also be of the formulae:
  • M and M' are independently selected from the group consisting of ruthenium and osmium, X, X 1 , L 2 , L 1 , R and R 1 are as previously defined, X and X are substituted or unsubstituted and are independently selected from the group from which X and X 1 are selected, R and R 1 are substituted or unsubstituted and are independently selected from the group from which R and R 1 are selected, L 1 is selected from the group from which L 1 is selected, L 2 is any bidentate, neutral electron donor ligand, and L 3 is any tetradentate, neutral electron donor ligand.
  • one aspect of the invention is a catalyst of the general structure:
  • the starting complexes may be selected from the following:
  • cumulated pentacoordinated complexes for example, those seen in complexes 1-4 (a, b), in the inventive process will produce inventive cumulated hexacoordinated complexes.
  • the cumulated complexes corresponding to complex 5 is as follows:
  • compounds 6-29 may also have corresponding cumulated complexes.
  • At least one of L, L 1 , L 1 , L 2 , X, X 1 , R and R 1 may be linked to at least one other of L, L 1 , L 1 , L 2 , X, X 1 , R and R 1 to form a bidentate or multidentate ligand array.
  • the inventive catalysts are made by contacting excess neutral electron donor ligand, such as a pyridine, with the previously described penta-coordinated metal carbene catalyst complex of the formula:
  • Ligands L and L may be the same compound, for example, pyridines (when excess pyridine is used), or may together form a bidentate ligand.
  • L 1 and L 1 may be the same, in which case, the pentacoordinated
  • the inventive complex may also be a cumulated carbene complex of the general formulas:
  • the inventive hexacoordinated catalyst complexes provide synthetic utility and utility in catalytic reactions. Without being bound by theory, these complexes contain substitutionally labile ligands, for example, pyridine and chloride ligands, and serve as a versatile starting material for the synthesis of new ruthenium metal carbene complexes.
  • the chloride ligands are more labile than in the corresponding pentacoordinated phosphine-based complexes.
  • X and X are any anionic ligand.
  • X and X 1 are selected from the group consisting of chloride, bromide, iodide, Tp, alkoxide, amide, and thiolate.
  • the pyridine ligands are more labile than the phosphines in the corresponding pentacoordinated phosphine-
  • L, L , L , and L can be any neutral electron donor ligands, including a NHC ligand. Depending on the size of the ligand, one or two neutral ligands (in addition to the NHC) may bind to the metal center.
  • inventive catalyst complexes may be used in both metathesis reactions or the formation of an NEC ligand based complex.
  • the hexacoordinated complex can lose a neutral electron donor ligand to produce the pentacoordinated catalyst complex.
  • the reaction may also proceed the other way to produce a hexacoordinated complex in the presence of excess L 2 .
  • the pentacoordinated complex may also lose the L 1 ligand to form the metathesis active tetracoordinated species (Scheme 5):
  • the L 1 ligand may also attach to a tetracoordinated species to form the pentacoordinated complex.
  • the tetracoordinated species may then initiate polymerization when in the presence of an olefin, as shown in Scheme 6, or may form the NHC-ligand based pentacoordinated complex when in the presence of a protected NHC-ligand (Scheme 7):
  • NHC- A-B indicates generally the protected form of a N- Heterocyclic Carbene (NHC).
  • the protected NHC- A-B may be of an unsaturated variety, such as
  • A is preferably H, Si, Sn, Li, Na, MgX 3 and acyl, wherein X 3 is any halogen, and B may be selected from the group consisting of CC1 3 ; CH 2 SO 2 Ph;
  • R is selected from the group consisting of Me, C 2 H 5 , i-C 3 H 7 , CH 2 CMe 3 , CMe 3 , C 6 H n (cyclohexyl), CH 2 Ph, CH 2 norbornyl, CH 2 norbornenyl, C 6 H 5 , 2,4,6-(CH 3 ) 3 C 6 H 2 (mesityl), 2,6-i-Pr 2 C 6 H 2 , 4-Me-C 6 IL; (tolyl), 4-Cl-C 6 H 4 ; and wherein R 22 and R 23 are independently selected from the group consisting of Me, C 2 H 5 , i-C 3 H 7 , CH 2 CMe 3 , CMe 3 , C 6 H n (cyclohexyl), CH 2 Ph, CH 2 norbornyl, CH 2 norbornenyl, C 6 H 5 , 2,4,6-(CH 3 ) 3 C 6 H
  • This approach relates to the thermal generation of a NHC ligand from a stable (protected) NHC derivative with a release of a quantity of A-B.
  • One of the more preferred methods to generate a reactive NHC ligand is to employ a stable carbene precursor where the A-B compound is also a reactive NHC ligand.
  • a detailed description of the protected NHC and related methods of synthesis and use canbe seen m U.S. Patent Application Nos. 10/107,531 and No. 10/138,188 the contents of each of which are inco ⁇ orated herein by reference.
  • the following structure for the sImesHCCl 3 shows a preferred embodiment of a protected NHC ligand for use with the inventive hexacoordinated complexes:
  • the NHC ligand based pentacoordinated complex may then lose the L ligand to form the metathesis active tetracoordinated species and proceed to initiate the polymerization reaction in the presence of an olefin (Scheme 8):
  • the hexacoordinated complex can undergo a ligand exchange such that the NHC replaces another neutral electron donor ligand resulting in an NHC ligand based hexacoordinated complex (Scheme 9):
  • Crystals suitable for X-ray crystal structure determination were grown by vapor diffusion of pentane into a saturated benzene solution of 31 at room temperature.
  • the collection and refinement parameters for the crystallographic analysis are summarized in Table 1.
  • the Ru-C(38) (N-heterocyclic carbene) bond length of 2.033(4) A is approximately 0.05 A shorter than that in complex 1, which is likely due to the relatively small size and moderate trans influence of pyridine relative to PCy 3 .
  • the 0.15 A difference in the Ru-C(l) and Ru-C(38) bond distances highlights the covalent nature of the former and the dative nature of the latter ruthenium-carbene bond.
  • the para-substituted triphenylphosphme derivatives 35, 36 and 37 (containing para substituents CF 3 , CI, and OMe, respectively) can be prepared using the inventive method.
  • the triarylphosphine ruthenium complexes 32, 35-37 are valuable catalysts as they are almost 2 orders of magnitude more active for olef ⁇ n metathesis reactions than the parent complex 1.
  • the electron-poor phosphine P(C 6 F 6 ) 3 shows no reaction with 31, even under forcing conditions.
  • the chlorine ligands of 31 are also substantially labile relative to those in the parent complex 1.
  • the reaction between 1 and Nal takes approximately 8 hours to reach completion under identical conditions.
  • 1H NMR spectroscopy reveals that the diiodide complex 38 contains only one pyridine ligand, while the analogous dichloride species 31 coordinates 2 equiv. of pyridine.
  • the relatively large size of the iodide ligands and the lower electrophilicity at the metal center in 38 are both believed to contribute to the formation of a five-coordinate complex in this system.
  • this ligand substitution proceeds by an associative mechanism.
  • Complex 31 reacts readily with phosphines, providing access to new complexes discussed herein.
  • Complex 31 also undergoes reaction with KO t - Bu, Nal, and KTp to provide new four-, five-, and six- coordinate ruthenium benzylidenes.
  • the inventive methodology is useful for facilitating the development of new ruthenium olefin metathesis catalysts containing structurally diverse ligand arrays.
  • inventive complexes are useful in olefin metathesis reactions, particularly for polymerization reactions.
  • These catalysts can be used in various metathesis reactions, including but not limited to, ring-opening metathesis polymerization of strained and unstrained cyclic olefins, ring-closing metathesis of acyclic dienes, acyclic diene metathesis polymerization ("ADMET"), self- and cross-metathesis reactions, alkyne polymerization, carbonyl olefination, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
  • ring-opening metathesis polymerization of strained and unstrained cyclic olefins ring-closing metathesis of acyclic dienes
  • ADMET acyclic diene metathesis polymerization
  • self- and cross-metathesis reactions self- and cross-metathesis reactions, alkyne polymerization, carbonyl ole
  • the most preferred olefin monomer for use in the invention is substituted or unsubstituted dicyclopentadiene (DCPD).
  • DCPD dicyclopentadiene
  • Various DCPD suppliers and purities may be used such as Lyondell 108 (94.6% purity), Veliscol UHP (99+% purity), B.F. Goodrich Ultrene ® (97% and 99% purities), and Hitachi (99+% purity).
  • olefin monomers include other cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclooctadiene (COD; DuPont); cyclooctene (COE, Alfa Aesar); cyclohexenylnorbornene (Shell); norbomene (Aldrich); norbomene dicarboxylic anhydride (nadic anhydride); norbornadiene (Elf Atochem); and substituted norbomenes including butyl norbomene, hexyl norbomene, octyl norbomene, decyl norbomene, and the like.
  • the olefinic moieties include mono-or disubstituted olefins and cycloolefins containing between 3 and 200 carbons.
  • metathesis-active olefinic moieties include substituted or unsubstituted cyclic or multicyclic olefins, for example, cyclopropenes, cyclobutenes, cycloheptenes, cyclooctenes, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclohexenes.
  • compositions include frameworks in which one or more of the carbon atoms carry substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphoms, antimony, or boron.
  • radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphoms, antimony, or boron.
  • the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
  • the olefin may be substituted with one or more groups such as C ⁇ -C 2 o alkyl, aryl, acyl, -C20 alkoxide, aryloxide, C 3 - C 20 alkyldiketonate, aryldiketonate, -C2 0 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, -C 20 alkylthio, arylthio, C 1 -C2 0 alkylsulfonyl, and -C20 alkylsulfinyl, Ci ⁇ o alkylphosphate, arylphosphate, wherein the moiety may be substituted or unsubstituted.
  • groups such as C ⁇ -C 2 o alkyl, aryl, acyl, -C20 alkoxide, aryloxide, C 3 - C 20 alkyldiketonate, aryldiketonate,
  • Examples of preferred polymerizable norbornene-type monomers include but are not limited to, norbomene (bicyclo[2.2.1]hept-2-ene), 5-methyl-2 -norbomene, ethylnorbornene, propylnorbornene, isopropylnorbornene, butylnorbornene, isobutylnorbornene, pentylnorbomene, hexylnorbornene, heptylnorbornene, octylnorbornene, decylnorbomene, dodecylnorbomene, octadecylnorbornene, p- tolylnorbornene, methyhdene norbomene, phenylnorbomene, ethylidenenorbomene, vinylnorbornene, exo-dicyclopentadiene
  • indanylnorbornene i.e., l,4,4,9-tetrahydro-l,4- methanofluorene, the reaction product of CPD and indene
  • 6,7, 10, 10-tetrahydro-7 10- methanofluoranthene
  • l,4,4,9,9,10-hexahydro-9,10[ ,2']-benzeno-l,4-methanoanthracene endo,endo-5,6- dimethyl-2-norbomene, endo,exo-5,6-dimethyl-2-norbomene, exo,exo-5,6-dimethyl- 2-norbornene, 1 ,4,4,5,6,9, 10, 13 , 14, 14-decahydro- 1 ,4-methanobenzocyclododecene (i.e., reaction product of CPD and 1,5,9-cyclod
  • olefin monomers may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition.
  • mixtures of cyclopentadiene dimer and trimers offer a reduced melting point and yield cured olefin copolymers with increased mechanical strength and stiffness relative to pure poly-DCPD.
  • incorporation of COD, norbomene, or alkyl norbomene co-monomers tend to yield cured olefin copolymers that are relatively soft and rubbery.
  • the resulting polyolefin compositions formed from the metathesis reactions are amenable to thermosetting and are tolerant of additives, stabilizers, rate modifiers, hardness and/or toughness modifiers, fillers and fibers including, but not limited to, carbon, glass, aramid (e.g., Kevlar ® and Twaron ® ), polyethylene (e.g., Spectra ® and Dyneema ® ), polyparaphenylene benzobisoxazole (e.g., Zylon ® ), polybenzamidazole (PBI), and hybrids thereof as well as other polymer fibers.
  • aramid e.g., Kevlar ® and Twaron ®
  • polyethylene e.g., Spectra ® and Dyneema ®
  • polyparaphenylene benzobisoxazole e.g., Zylon ®
  • polybenzamidazole PBI
  • the metathesis reactions may optionally include formulation auxiliaries.
  • auxiliaries include antistatics, antioxidants (primary antioxidants, secondary antioxidants, or mixtures thereof), ceramics, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity- increasing agents, and demolding enhancers.
  • fillers for improving the optical physical, mechanical, and electrical properties include glass and quartz in the form of powders, beads, and fibers, metal and semi-metal oxides, carbonates (e.g. MgCO 3 , CaCO 3 ), dolomite, metal sulfates (e.g. gypsum and barite), natural and synthetic silicates (e.g. zeolites, wollastonite, and feldspars), carbon fibers, and plastics fibers or powders.
  • the UN and oxidative resistance of the polyolefin compositions resulting from the metathesis reactions using the inventive carbene complex may be enhanced by the addition of various stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered amine light stabilizers or HALS), and UN light absorbers (e.g., hydroxy benzophenone absorbers, hydroxyphenylbenzotriazole absorbers, and the like), as described in U.S. Application No. 09/498,120, filed February 4, 2000, the contents of which are incorporated herein by reference.
  • stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered
  • Exemplary primary antioxidants include, for example, 4,4'-methylenebis (2,6-di- tertiary-butylphenol) (Ethanox 702 ® ; Albemarle Corporation), l,3,5-trimethyl-2,4,6- tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330 ® ; Albermarle Corporation), octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate (Irganox 1076 ® ; Ciba-Geigy), and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate)(Irganox ® 1010; Ciba-Geigy).
  • Ethanox 702 ® Albemarle Corporation
  • Exemplary secondary antioxidants include tris(2,4-ditert-butylphenyl)phosphite (Irgafos ® 168; Ciba-Geigy), l:ll(3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wingstay ® SN-1; Goodyear), and the like.
  • Exemplary light stabilizers and absorbers include bis(l, 2,2,6,6- pentamethyl-4-piperidinyl)-[[3,5-bis(l,l-dimethylethyl)-4- hydroxyphenyl]methyl]butylmalonate (Tinuvin ® 144 HALS; Ciba-Geigy), 2-(2H- benzotriazol-2-yl)-4,6-ditertpentylphenol (Tinuvin ® 328 absorber; Ciba-Geigy), 2,4- di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenyl (Tinuvin ® 327 absorber; Ciba- Geigy), 2-hydroxy-4-(octyloxy)benzophenone (Chimassorb ® 81 absorber; Ciba- Geigy), and the like.
  • a suitable rate modifier such as, for example, triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, triarylphosphites, mixed phosphites, or other Lewis base, as described in U.S. Patent No. 5,939,504 and U.S. Application No. 09/130,586, the contents of each of which are herein inco ⁇ orated by reference, may be added to the olefin monomer to retard or accelerate the rate of polymerization as required.
  • TPP triphenylphosphine
  • TPP triphenylphosphine
  • tricyclopentylphosphine tricyclohexylphosphine
  • triisopropylphosphine trialkylphosphites
  • triarylphosphites triarylphosphites
  • mixed phosphites or other Lewis base
  • the resulting polyolefin compositions, and parts or articles of manufacture prepared therefrom may be processed in a variety of ways including, for example, Reaction Injection Molding (RIM), Resin Transfer Molding (RTM) and vacuum-assisted variants such as NARTM (Vacuum- Assisted RTM) and SCRIMP (Seemann Composite Resin Infusion Molding Process), open casting, rotational molding, centrifugal casting, filament winding, and mechanical machining.
  • RIM Reaction Injection Molding
  • RTM Resin Transfer Molding
  • NARTM Vauum- Assisted RTM
  • SCRIMP Seemann Composite Resin Infusion Molding Process
  • the metathesis reactions may occur in the presence or absence of a solvent.
  • solvents that can be used in the polymerization reaction include organic, protic, or aqueous solvents, which are preferably inert under the polymerization conditions.
  • solvents include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof.
  • Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, water or mixtures thereof.
  • the solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, or mixtures thereof.
  • the solvent is toluene, or a mixture of benzene and methylene chloride.
  • the inventive complexes have a well-defined ligand environment that enables flexibility in modifying and fine-tuning the activity level, stability, solubility and ease of recovery of these catalysts.
  • the solubility of the carbene compounds may be controlled by proper selection of either hydrophobic or hydrophilic ligands as is well known in the art.
  • the desired solubility of the catalyst will largely be determined by the solubility of the reaction substrates and reaction products.
  • the inventive metal carbene complexes have shown a high rate of initiation allowing for most, if not all, of the complex added to the reaction to be consumed. Thus, less catalyst is wasted in the metathesis reaction. In contrast, the previous pentacoordinated initiators had a higher amount of extractibles (i.e. unpolymerized monomer) remaining after the reaction concluded. The rate of propogation is also slowed by the presence of the two pyridine ligands. The high rate of initiation and low rate of propogation yields polymers with narrow polydisperities relative to those achieved with the earlier pentacoordinated complexes. Moreover, it was determined that heat increases the rate of the initiation.
  • Thermal initiation of the pentacoordinated complexes can be seen in U.S. Patent No. 6,107,420, the contents of which are inco ⁇ orated herein by reference.
  • the initiation and/or rate of the metathesis polymerization using the inventive catalysts is controlled by a method comprising contacting the inventive catalyst with an olefin and heating the reaction mixture.
  • the T max for the thermal initiation of the inventive catalyst is significantly higher than the T ma ⁇ for the previous pentacoordinated catalysts.
  • T max reduces the need for post cure. Additionally, even if peroxides or radicals are added to promote crosslinking, the degree of crosslinking in the part that uses the radical mechanism is increased in comparison to a part prepared using the previous pentacoordinated metathesis catalysts. Moreover, the half-life is dependent on the maximum temperature. Using the inventive catalysts, the half life is reduced substantially, and therefore less catalyst is needed, providing a significant commercial advantage. Without being bound by theory, the higher T max indicates that in a ROMP reaction, more rings are opened, and there is a better degree of cure. With a higher T ma ⁇ , the extractibles are almost to zero, indicating that almost every molecule that can be reacted is reacted.
  • the vinylidenes are advantageous in that they are more stable at higher temperatures than the alkylidenes.
  • the protected NHC e.g., a saturated Imes ligand as described in U.S. Provisional Patent Application Nos. 60/288,680 and 60/278,311, the contents of each of which are inco ⁇ orated herein by reference
  • the time to reach the peak is significantly reduced.
  • a high peak exotherm means more catalyst is available for polymerization, indicating that the extractibles are close to zero. Accordingly, the inventive catalysts have better conversion, better properties, even in the presence of fillers and additives.
  • Pentane, toluene, benzene, and benzene-c? 6 were dried by passage through solvent purification columns. Pyridine was dried by vacuum transfer from CaH 2 . All phosphines as well as KTp were obtained from commercial sources and used as received. Ruthenium complexes 1-4 and 44-48 were prepared according to literature procedures.
  • Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 2- pyridinecarboxaldehyde (1.01 grams, 4 mol equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 °C to about 25 °C during which time a color change from dark pu ⁇ le to dark blue was observed. The reaction mixture was transferred into 75 mL of cold (about 0 °C) pentane, and a dark blue solid precipitated.
  • T max Time to reach maximum temperature
  • T max 200.9 °C.
  • Glass transition temperature measured by thermal mechanical analysis (TMA) 145 °C.
  • Percent residual monomer (toluene extraction at room temperature) 4.57 %.
  • KTp (87 mg, 0.34 mmol) and complex 31 (125 mg, 0.17 mmol) were combined in CH 2 CI 2 (10 mL) and stirred for 1 hour.
  • Pentane (20 mL) was added to precipitate the salts, and the reaction was stirred for an additional 30 min and then cannula filtered.
  • the resulting bright green solution was concentrated, and the solid residue was washed with pentane (2 x 10 mL) and methanol (2 x 10 mL) and dried under vacuum to afford 43 (84 mg, 66% yield) as an analytically pure green powder.
  • Crystal, intensity collection, and refinement details were summarized in Table 1.
  • the selected crystal was mounted on a glass fiber with Paratone-N oil and transferred to a Bruker SMART 1000 CCD area detector equipped with a Crystal Logic CL24 low- temperature device. Data were collected with ⁇ -scans at seven ⁇ values and subsequently processed with SAINT. No abso ⁇ tion or decay corrections were applied.
  • SHELXTL was used to solve (by direct methods and subsequent difference Fourier maps) and to refine (full-matrix least-squares on F 2 ) the structure. There are two molecules in the asymmetric unit.
  • T max Time to reach maximum temperature
  • T max 246.2 °C.
  • Glass transition temperature measured by thermal mechanical analysis (TMA) 175.35 °C.
  • TMA thermal mechanical analysis
  • Example (2) A 75 g mass of hexylnorbornene was polymerized using

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Abstract

L'invention concerne de nouveaux catalyseurs de métathèse hexacoordonnés et leurs procédés de fabrication et d'utilisation. Ces catalyseurs sont représentés par la formule suivante, dans laquelle M représente ruthénium ou osmium; X et X1 sont identiques ou différents et représentent chacun individuellement un ligand anionique; L, L?1' et L2¿, identiques ou différents, représentent chacun individuellement un ligand neutre donneur d'électrons; et R et R1 représentent chacun individuellement hydrogène ou un substituant choisi dans le groupe comprenant C¿1 ?C20 alkyle, C2 C20 alcényle, C2 C20 alkynyle, aryle, C1 C20 carboxylate, C1 C20 alcoxy, C2 C20 alcényloxy, C2 C20 alkynyloxy, aryloxy, C2 C20 alcoxycarbonyle, C1 C20 alkylthio, C1 C20 alkylsulfonyle et C1 C20 alkylsulfinyle et silyle. Eventuellement, chaque groupe substituant R ou R?1¿ peut être substitué par au moins un groupe caractéristique choisi dans le groupe comprenant C¿1 ?C10 alkyle, C1 C10 alcoxy et aryle, chacun pouvant également être substitué par au moins un groupe choisi dans halogène, C1 C5 alkyle, C1 C5 alcoxy et phényle. De plus, un quelconque des ligands catalyseurs peut également comprendre au moins un groupe fonctionnel. Ces groupes fonctionnels peuvent comprendre notamment hydroxyle, thiol, thioéther, cétone, aldéhyde, ester, éther, amine, imine, amide, nitro, acide carboxylique, disulfide, carbonate, isocyanate, carbodiimide, carboalcoxy, carbamate, halogène, alcool, acide sulfonique, phosphine, imide, acétal, cétal, boronate, cyano, cyanohydrine, hydrazine, énamine, sulfone, sulfide et sulfényle. Dans certains modes de réalisation, au moins un des L, L?1' et L2¿ représente un ligand de carbène N-hétérocyclique.
EP02791535.4A 2001-08-01 2002-06-14 Catalyseurs de metathese de carbene metallique de ruthenium ou d'osmium hexacoordonnes Expired - Lifetime EP1423195B1 (fr)

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US107531 1979-12-27
US30980601P 2001-08-01 2001-08-01
US309806P 2001-08-01
US31497801P 2001-08-24 2001-08-24
US314978P 2001-08-24
US09/948,115 US6610626B2 (en) 2000-09-05 2001-09-05 Highly active metathesis catalysts generated in situ from inexpensive and air stable precursors
US948115 2001-09-05
US17489 2001-12-14
US10/017,489 US6759537B2 (en) 2001-03-23 2001-12-14 Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts
US138188 2002-03-05
US10/107,531 US6838489B2 (en) 2001-03-23 2002-03-25 High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor
US10/138,188 US20030083445A1 (en) 2001-03-23 2002-05-03 High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor
PCT/US2002/019167 WO2003011455A1 (fr) 2001-08-01 2002-06-14 Catalyseurs de metathese de carbene metallique de ruthenium ou d'osmium hexacoordonnes

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